Abstract
In a companion paper (Kroll, J. H.; Clarke, J. S.; Donahue, N. M.; Anderson, J. G.; Demerjian, K. L. J. Phys. Chem. A 2001, 105, 1554) we present direct measurements of hydroxyl radical (OH) yields for the gas-phase reaction of ozone with a number of symmetric alkenes. Yields are strongly pressure-dependent, contrary to the results of prior scavenger studies. Here we present a statistical-dynamical model of OH production from the reaction, utilizing RRKM/master equation calculations to determine the fate of the carbonyl oxide intermediate. This model agrees with our experimental results, in that both theory and observations indicate strongly pressure-dependent OH yields. Our calculations also suggest that ethene ozonolysis produces OH via a different channel than the substituted alkenes, though the identity of this channel is not clear. This channel may play a role in the ozonolysis of monosubstituted alkenes as well. Our time-dependent master equation calculations show that the discrepancy between OH yie...
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